Self-assembly of mercaptane-metallacarborane complexes by an unconventional cooperative effect: a C-H...S-H...H-B hydrogen/dihydrogen bond interaction

The existence of a dihydrogen bond (S-H...H-B) and its combination with a C-H...S hydrogen bond in an unusual cooperative effect are demonstrated from a combination of experimental and theoretical methods. This cooperative effect seems to be responsible for self-assembly of mercaptane-metallacarborane complexes such as closo-[3-Ru(eta6-C6H6)-8-HS-1,2-C2B9H10] (1) and closo-[3-Co(eta5-C5H5)-8-HS-1,2-C2B9H10] (3), which present identical supramolecular two-dimensional polymeric networks. The findings, besides documenting structurally the first S-H...(H-B)2 dihydrogen bond and the unconventional cooperative ability of a boron-attached SH group, prove that substituted carboranes have the potential to serve as building blocks for assembling complex structures.     

Phase equilibrium and thermophysical properties of mixtures containing a cyclic ether and 1-chloropropane

The phase equilibrium, at T = 298.15 and 313.15 K and several thermophysical properties (density, sound velocity, refractive index) at T = 283.15, 298.15 and 313.5 K of mixtures formed by a cyclic ether (tetrahydropyran, tetrahydrofuran) and 1-chloropropane has been studied. Excess Gibbs functions, excess volumes, excess isentropic compressibilities and refractive index deviations have been obtained from the experimental data. Both the molecular characteristics of the pure compounds and the molecular interactions in the mixing process have been used to analyse the results.     

Biomimetic synthesis of petuniasterone D via the epoxy ester[bond]ortho ester rearrangement

The side chain of the insecticidal steroid petuniasterone D was synthesized by the biomimetic acid-catalyzed epoxy ester[bond]ortho ester rearrangement. In addition to the natural (22R,24R)-configuration of the side chain ortho ester, compounds bearing the epimeric (22R,24S)-, (22S,24R)-, and (22S,24S)- [3.2.1]-bicyclic ortho esters were also produced by stereospecific rearrangement of the corresponding isomeric epoxy esters. Functionalization of the steroid nucleus of the (22R,24R)-ortho ester completed the synthesis of the natural product.     

Routine analysis by high precision gas chromatography/mass selective detector/isotope ratio mass spectrometry to 0.1 parts per mil

Stable isotope methods are potentially quite useful for validating natural or enhanced mineral degradation of contaminants. For this reason, a continuous flow gas chromatograph (GC), isotope ratio mass spectrometer (IRMS) has been coupled with a quadrupole mass selective detector (MSD) to allow simultaneous mass spectral and stable carbon isotope ratio data to be obtained from a single chromatographic analysis. This allows the target contaminant and any extra-cellular degradation intermediates to be both qualified and quantified. Previously acceptable limits of precision (0.3 parts per mil) are undesirable given the small fractionation observed during aerobic degradation. To further understand the fate of organic contaminants and to gain information about the metabolic degradative pathway employed by a microorganism, routine isotopic analyses on a range of analytes have been performed. Quantities of sample producing mass-44 ion beam signal (I(44)) of 2 x 10(-10) to 1 x 10(-8) A were analysed. When the IRMS was tuned for high sensitivity, ion source nonlinearities were overcome by peak height correction from an algorithm that was produced using known isotopic standards of varying concentrations. This led to sample accuracy of <0.01 per thousand and sample precision of 0.1 per thousand. Copyright 1999 John Wiley & Sons, Ltd.     

Frequency scan for the analysis of high mass ions generated by matrix-assisted laser desorption/ionization in a paul trap

An ion trap has been modified for the analysis of high mass ions generated by matrix-assisted laser desorption/ionization. Samples are deposited on a probe tip and introduced directly onto the hyperbolically shaped surface of one endcap. All three electrodes - both the endcaps and the ring electrode - are insulated so that the radio frequency (Rf) voltage may be applied to the center ring electrode and the inverted Rf voltage to the endcaps. By using low frequencies (below 100 kHz) and low amplitudes (below 200 V), high mass singly charged ions may be trapped and analyzed by a frequency sweep at constant amplitude. In the high mass range (60-160 kDa), this instrument showed good sensitivity, signal-to-noise ratios, and mass resolution. Copyright 1999 John Wiley & Sons, Ltd.     

Study of the Surface Tensions of Cyclohexane or Methylcyclohexane with Some Cyclic Ethers

Experimental surface tensions, measured with a drop volume tensiometer and the corresponding surface tension deviations for the binary mixtures of cyclohexane or methylcyclohexane with a cyclic ether (tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran or 2,5-dimethyltetrahydrofuran) are given at 25 and 40 C. The results have been discussed in terms of lyophobicity and molecular interactions using the extended Langmuir isotherm. The model proposed by Patterson and Rastogi has been used to calculate the surface tensions of the pure components and of their mixtures at 25C; these calculations have been compared with the experimental results.     

Subdifferentiation of integral functionals

Mathematical Programming - We examine how the subdifferentials of nonconvex integral functionals can be deduced from the subdifferentials of the corresponding integrand or at least be estimated...     

Microwave absorption studies of MgB2 superconductor

Microwave absorption studies have been carried out on MgB₂ superconductor using a standard X-band EPR spectrometer. The modulated low-field microwave absorption signals recorded for polycrystalline (grain size ∼ 10 μm) samples suggested the absence of weak-link character. The field dependent direct microwave absorption has been found to obey a ✓H dependence with two different slopes, which indicated a transition from strongly pinned lattice to flux flow regime.     

Plasmonic Surfaces for Cell Growth and Retrieval Triggered by Near‐Infrared Light

Methods for efficient detachment of cells avoiding damage are required in tissue engineering and regenerative medicine. We introduce a bottom–up approach to build plasmonic substrates using micellar block copolymer nanolithography to generate a 2D array of Au seeds, followed by chemical growth leading to anisotropic nanoparticles. The resulting plasmonic substrates show a broad plasmon band covering a wide part of the visible and near‐infrared (NIR) spectral ranges. Both human and murine cells were successfully grown on the substrates. A simple functionalization step of the plasmonic substrates with the cyclic arginylglycylaspartic acid (c‐RGD) peptide allowed us to tune the morphology of integrin‐rich human umbilical vein endothelial cells (HUVEC). Subsequent irradiation with a NIR laser led to highly efficient detachment of the cells with cell viability confirmed using the MTT assay. We thus propose the use of such plasmonic substrates for cell growth and controlled detachment using remote near‐IR irradiation, as a general method for cell culture in biomedical applications.